Photoelectrode and Method for Preparing the Same

ABSTRACT

The present invention relates to an photoelectrode and the preparation method thereof, wherein said photoelectrode comprises a substrate and a titania layer composed of a mesoporous titania bead having a diameter of 200-1000 nm, specific surface area of 50-100 m 2 /g, porosity of 40-60%, pore radius of 5-20 nm, pore volume of 0.20-0.30 cm 3 /g, and the titania comprised in the bead is anatase titania.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photoelectrode and method forpreparing the same.

2. Description of the Related Art

After industrial revolution, fossil fuel consumptions grew dramaticallyaccompanying with the development of science, and resulted in fossilfuel exhaustion and environmental damages. For sustainable survival, thedevelopment of renewable and alternative energy was the ultimate goal ofthe world. In all alternative energies, solar energy caught people'sattention because it was abundant and clean, and many companies hadinvested in the associated research and development.

Solar cell, also called photovoltaic cell, was a device for convertinglight energy into electrical energy. However, lots of energy wasconsumed during the manufacture of solar cells, so it was still achallenge for solar cells to reach grid parity. At present, mostcommercial solar cells were silicon solar cells, in whichmonocrystalline silicon solar cells and multicrystalline silicon solarcells had a cell efficiency of 18% and 17%, respectively. But the costof silicon solar cells was high because pure crystalline siliconmaterials were widely used in semiconductor industry. Materialsgenerally used for non-silicon thin-film solar cells were cadmiumtelluride (CdTe) or copper indium gallium diselenide (CIGS, CuInGaSe),in which the former material was mainly used by First Solar formanufacturing solar cells with the lowest price per watt in allcommercial solar cells, but cadmium contamination was a concerned issue;and the latter material could be used for manufacturing stable solarcells with high efficiency and long life span, but the complicatedelement composition caused low yield rate.

A solar cell promising for dramatically reducing electricity cost wasdye-sensitized solar cell (DSC), which was published on Nature in 1991(B. Oregan and M. Grätzel, “A Low-Cost, High-Efficiency Solar-Cell BasedOn Dye-Sensitized Colloidal TiO₂ Films,” Nature, 353 (6346), 737-740,1991). DSC had advantages that it cost less and could be applied toflexible applications. Comparing with silicon solar cells, it was lessinfluenced by incident angle and increased temperature, so the DSC wasvery competitive and potential to lead the trend of the next generationsolar cells. There had been many commercial DSCs in the market, forexample, Sharp had manufactured a DSC having a high cell efficiency of10.4%. Generally, DSC had a shorter life span and lower cell efficiency;however, if these disadvantages were overcome, it would be the mostwidely used solar cell in the future.

In DSCs, the photoelectrode was important for loading dye molecules andtransferring electrons, and it was the key to decide cell efficiency.The main material for producing the photoelectrode was titaniananoparticles. Titania (TiO₂) was a stable, non-toxic material with highrefractive index (n=2.4-2.5), and widely used in our daily life, such asin white pigment, tooth paste, cosmetics or food. The naturallyoccurring titania had three main crystal phases: rutile, anatase andbrookite, in which the rutile titania was the most stable crystal phasein view of thermodynamics; but the anatase titania was suitable for cellapplications because it had a greater energy band gap and a higherconduction band, so the anatase titania could reach a greaterquasi-Fermi energy level and open circuit voltage under the sameelectron concentration, thereby achieving a better cell efficiency.

Regarding with the morphology of titania, the titania nanoparticles(NPs) was widely applied to DSCs because it had a high specific surfacearea which was able to absorb a large amount of dye. However, NPs didnot have an oriented structure, and the electrons immigrated in randomdirections, so the electron collection efficiency was limited. Inaddition, the particle size of NPs was too small to produce effectivevisible light scattering and good light harvesting. Therefore, manystrategies had been taken to solve this problem, for example, M.Zukalova et al. produced an oriented particle by polymer template methodand the resulted cell efficiency was higher than that of non-orientedparticle by 1.3% (Nano Letters, 5 (9), 1789-1792, 2005); J. M. Macak etal. prepared a TiO₂ nanotube with high aspect ratio by anodization(Angewandte Chemie-International Edition, 44 (14), 2100-2102, 2005) andJ. R. Jennings et al. produced a photoelectrode from TiO₂ nanotube andtitanium substrate, giving a electron collection efficiency of nearly100% (Journal of the American Chemical Society, 130 (40), 13364-13372,2008), which demonstrated that tubular or linear structures provide abetter diffusion direction for electrons; and K. Shankar et al. provedthat when a glass substrate was used instead, the cell efficiency wouldreached 6.1% (Nano Letters, 8 (6), 1654-1659, 2008). Nevertheless, thestructure of nanotube and the like did not provide sufficientdye-loading, so the other structures derived from nanoparticles werestill under research and development.

Another way to solve the low dye-loading problem was to use thestructure called TiO₂ beads (see D. H. Chen et al., Advanced Materials,21 (21), 2206, 2009 and Y. J. Kim et al., Advanced Materials, 21 (36),3668, 2009). The TiO₂ bead with submicron-meter size had the followingadvantages: (1) this bead dramatically increased light harvestingefficiency because its size was large enough for Mie scattering, so thelight route in the photoelectrode lengthens and dye loading increased;(2) this bead had a large surface area, which helped dye loading; (3)TiO₂ bead had regular mesopores that increased electron transfer andhelped mass transfer of electrolyte. However, this two-layerphotoelectrode was only applied to rigid DSCs, not introduced intoflexible dye-sensitized solar cells (FDSCs). This was because there wereless contacts between large size TiO₂ beads and the substrate, so thephotoelectrode was not well-attached on the substrate, and thishighlighted the disadvantage of FDSCs. In recent studies, the best cellefficiency of the flexible low-temperature glass DSCs using TiO₂ beadswas 6.3% (S. H. Jang et al., Electrochemistry Communications, 12 (10),1283-1286, 2010). TiO₂ was not used in the general flexible plasticsubstrates because the plastic substrates could only be processed at150° C. or less and they could not bear the high temperature treatmentfor removing organic compounds and sintering TiO₂ beads on thetraditional rigid substrates (about 450° C.). Therefore, the DSCs usingTiO₂ beads had low electron collection efficiency and reduced cellefficiency.

SUMMARY OF THE INVENTION

The inventors were the first to use mesoporous titania beads formanufacturing the photoelectrode of cells, and they surprisingly foundthat the anatase TiO₂ comprised in the mesoporous titania beads and theoriented attachment between crystal grains increased electron diffusion.In addition, the TiO₂ beads with submicron-meter size of the presentinvention resulted in excellent light scattering. With these advantages,the titania bead of the present invention can be used to give highefficiency cells.

One object of the present invention is to provide a photoelectrodecomprising a titania layer composed of a mesoporous titania bead, andsaid mesoporous titania bead comprises anatase titania, which providesexcellent light scattering and increases dye-loading.

Another object of the present invention is to provide a method forpreparing the photoelectrode, wherein a titania layer composed of amesoporous titania bead is formed on a substrate.

To achieve these objects, the present invention provides aphotoelectrode, comprising (1) a substrate; and (2) a titania layercomposed of a mesoporous titania bead having a diameter of 200-1000 nm,specific surface area of 50-100 m²/g, porosity of 40-60%, pore radius of5-20 nm, pore volume of 0.20-0.30 cm³/g, and the titania comprised inthe bead is anatase titania.

In a preferred embodiment, said mesoporous titania bead has a diameterof 500-1000 nm; and more preferably, 750-1000 nm.

In a preferred embodiment, said mesoporous titania bead has a porosityof 50%.

In a preferred embodiment, the titania layer has a thickness of 5-10 μm;more preferably, 7.5-8 μm.

In a preferred embodiment, said substrate is a metal substrate, or atransparent non-conductive substrate covered by a transparent conductivefilm. Preferably, said transparent non-conductive substrate is a plasticor glass substrate, and said transparent conductive film is ITO, FTO orother transparent conductive oxide (TCO) film; more preferably, saidplastic substrate is PEN or PET substrate; and most preferably, thesubstrate of the present invention is ITO-PEN substrate, ITO-glasssubstrate, FTO-PEN substrate, titanium substrate or stainless steelsubstrate.

In a preferred embodiment, said mesoporous titania bead is prepared bythe following steps:

(1) adding a steric agent and a titanium-containing precursor intoethanol to proceed sol-gel reaction and give a sol-gel product, whereinthe molar ratio of said steric agent:said titanium-containingprecursor:ethanol is 0.1-1:1:200-300; and

(2) heating said sol-gel product in water at 120-200° C. for 1-24 hoursto obtain the mesoporous titania bead.

In a preferred embodiment, said steric agent is a tertiary amine; morepreferably, said steric agent is selected from hexamine, trimethylamine((CH₃)₃N), quinoline (C₉H₇N), isoquinoline (C₉H₇N) or methyldiethylamine(CH₃N(CH₂CH₃)); and most preferably, said steric agent is hexamine.

In a preferred embodiment, said titanium-containing precursor isselected from titanium tetraisopropoxide, titanium tetrachloride,titanium trichloride, ethyl orthotitanate or Ti(OC₄H₈)₄; and mostpreferably, said titanium-containing precursor is titaniumtetraisopropoxide (TTIP).

In a preferred embodiment, said step (2) is preferably conducted at atemperature of 160-200° C.; more preferably, at 200° C.

In a preferred embodiment, the method further comprises adding a saltinto said ethanol in step (1) to adjust ionic strength to1×10⁻⁴-32×10⁻⁴; more preferably, said salt is selected from KCl, LiCl,KCl, LiF, NaF, KF, LiBr, NaBr, KBr, LiI, NaI, KI, CsCl, CsI, CsBr, KNO₃;and most preferably, said salt is KCl.

In a preferred embodiment, said titania layer increases scatteringefficiency and used as a scattering layer.

In a preferred embodiment, a titania nanoparticle layer is furthercomprised between said substrate and said titania layer; preferably,said titania nanoparticle layer has a thickness of 3-5 μm.

In a preferred embodiment, said titania nanoparticle layer is composedof a titania nanoparticle, not composed of said mesoporous titania bead;more preferably, said titania nanoparticle of the titania nanoparticlelayer is P25, ST-01, ST-21, ST-31, TTO-55S or ST-30L.

In a preferred embodiment, said photoelectrode is used for manufacturinga cell.

The present invention also provides a method for preparing theabove-mentioned photoelectrode, comprising:

(1) providing a substrate;

(2) coating a mesoporous titania bead on said substrate to obtain acoated layer, in which said bead has a diameter of 200-1000 nm, specificsurface area of 50-100 m²/g, porosity of 40-60%, pore radius of 5-20 nm,pore volume of 0.20-0.30 cm³/g, and the titania comprised in the bead isanatase titania; and

(3) pressing the coated layer from step (2) under room temperature toobtain said titania layer.

In a preferred embodiment, said substrate provided in theabove-mentioned method is a metal substrate, or a transparentnon-conductive substrate covered by a transparent conductive film.Preferably, said transparent non-conductive substrate is a plastic orglass substrate, and said transparent conductive film is ITO, FTO orother transparent conductive oxide (TCO) film; more preferably, saidplastic substrate is PEN or PET substrate; and most preferably, thesubstrate is ITO-PEN substrate, ITO-glass substrate, FTO-PEN substrate,titanium substrate or stainless steel substrate.

In a preferred embodiment, the above-mentioned method further comprisesthe following step between step (1) and step (2): coating a titaniananoparticle on said substrate to obtain a titania nanoparticle layer,and said titania nanoparticle is not said mesoporous titania bead;preferably, said titania nanoparticle of the titania nanoparticle layeris P25, ST-01, ST-21, ST-31, TTO-55S or ST-30L.

In a preferred embodiment, the above-mentioned method is applied to cellmanufacture.

The present invention has proved that the properties of titania, such ascrystallinity, surface oxygen vacancy concentration and the like, affectdiffusion and life span of electrons, thereby affecting chargecollection efficiency. And, the size of titania bead apparently affectsthe efficiency of light harvesting and electron injection, therebyaffecting the cell efficiency. The mesoporous titania bead, or themesoporous titania bead prepared by the method of the present invention,has a proper size, good crystallinity and low surface oxygen vacancyconcentration. Moreover, it is also potential to be used as a scatteringlayer, which is suitable for manufacturing photoelectrode of cells, andenhancing cell efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1(A) shows the XRD diffraction diagrams of the sol-gel products (S)obtained by using different amount of steric agent. FIGS. 1(B)-1(D) showthe XRD diffraction diagrams of the titania products of the presentinvention (H). The first number after the letter “H” represents theamount of steric agent, and the second number represents thewater-heating temperature.

FIG. 2 shows the HRTEM image of the mesoporous titania bead prepared byusing 0.75 g steric agent and heating at 200° C. in water-heatingtreatment in the present invention.

FIG. 3(A) shows the XRD diffraction diagrams of the titania beadsprepared by using different amount of steric agent and heated atdifferent temperature in water-heating step in the present invention.FIG. 3(B) shows the XRD diffraction diagrams of the commercial titaniapowders, P25 and ST41.

FIG. 4 shows the SEM images of the titania products prepared by using(A) 0.25 g, (B) 0.50 g, (C) 0.75 g of steric agent and heated at 200° C.in water-heating step in the present invention.

FIG. 5(A) shows the schematic illustration of photoelectrode comprisinga scattering layer and a titania nanoparticle layer. FIG. 5(B) shows theschematic illustration of photoelectrode comprising single titanialayer. FIG. 5(C) shows the amplified schematic illustration ofphotoelectrode composed of the commercial titania P25 and the comprisingtitania beads of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

All scientific terms hereinafter are given their ordinary meaning in theusage of the field of the invention, unless the text of the patent makesclear that a term is used with a special meaning.

The term “titania layer” used herein refers to a TiO₂ layer prepared bythe mesoporous titania beads of the present invention, which is able toincrease scattering efficiency and used as a scattering layer. Thetitania layer has a thickness of 5-10 μm, preferably, 7.5-8 μm.

The term “titania nanoparticle layer” used herein refers to a TiO₂ layerprepared by titania nanoparticles, and said titania nanoparticles arenot the mesoporous titania beads of the present invention or themesoporous titania beads prepared by the method of the presentinvention. The titania nanoparticle can be a commercial nanoparticle,such as P25, ST-01, ST-21, ST-31, TTO-55S and ST-30L, and the titaniananoparticle layer has a thickness of 3-5 μm.

The term “substrate” used herein refers to a conductive substrate,comprising but not limit to: a metal substrate, and a transparentnon-conductive substrate covered by a transparent conductive film.Preferably, said transparent non-conductive substrate covered by atransparent conductive film is a plastic or glass substrate covered by atransparent conductive film. More preferably, said transparentconductive film is ITO, FTO or other transparent conductive oxide (TCO)film; and said plastic substrate is PEN or PET substrate. The examplesof the substrate used in the present invention are ITO-PEN substrate,ITO-glass substrate, FTO-PEN substrate, titanium substrate, stainlesssteel substrate.

Preparation of the Titantia Products of the Present Invention

The titania products of the present invention were prepared by a noveltwo-step process, comprising the first sol-gel reaction step, and thesecond water-heating treatment step.

(1) Sol-Gel Reaction

First, 0.25 g, 0.50 g or 0.75 g of the steric agent, hexamine (Riedel-dehaen, 99.5%), was added into 200 mL of ethanol (J-T baker, 99.9%), andstirred with a magnetic bar. Several minutes later, 1 mL KCl ionicsolution (0.1M) prepared by solid KCl (SHOWA, 99.5%) was added intohexamine solution in ethanol to adjust the ionic strength. Severalminutes later, hexamine is dissolved completely, and 4.4 mL of thetitanium-containing precursor, titanium tetraisopropoxide (TTIP)(Acros, >98%) was added to start hydrolysis reaction, and the solutionwas turned from transparent into white in minutes, which showed theproceeding of condensation reaction. The solution was further stirredfor several minutes and stood for one day to complete the sol-gelreaction. On the next day, the solution was filtered and dried, andground to give an amorphous white powder (TiO_(x)), which was named as asol-gel product hereinafter.

(2) Water-Heating Treatment

0.4 g of the sol-gel product obtained from the previous step was addedinto 25 mL of deionized water and stirred for several minutes, and thenthe mixture was placed in autoclave and stayed at 120° C., 160° C. or200° C. for 6 hours to proceed water-heating treatment. After that, thesolution was filtered and dried to obtain a crystallized white powder,namely, the titania product of the present invention.

Preparation of Photoelectrode

The titania product of the present invention and a commercial titaniapowder P25 (Degussa) were used for the following preparations.

First, a titania slurry was prepared. The above-mentioned two titaniahad different surface characteristics, so different formulations wereused for their preparations: 0.6 g of P25 powder, 100 μL of acetic acid(J-T baker, 99.9%), 0.5 mL of deionized water, 2.5 mL of ethanol and 4mL of tert-butanol (Merck, >99%) were mixed, and stirred and sonicatedalternating to obtain a homogeneous and thick P25 slurry. In addition,0.3 g of the titania product of the present invention, 1.5 mL of ethanoland a trace of HCl (Aldrich, 37%) were mixed, then the titania slurry ofthe present invention was prepared by the steps the same as the previousdescription.

An appropriate amount of the titania slurry of the present invention (orP25 slurry) was dropped on a ITO-PEN substrate, and spin-coated by atwo-step spin-coating process: the first step was proceed at 700 rpm for20 seconds, and the second step wad proceed at 1500 rpm for 20 seconds.After that, the coated substrate was dried naturally. The spin-coatingprocess was repeated until the titania coating has a desired thickness,and then the coating was scraped into a size of 4×4 mm square (0.16cm²). Then the pressing step under room temperature was taken, whichmeans a pressure of 50 kg/cm² was given in a direction from the titaniacoating to the ITO-PEN substrate for 5 minutes to enhance the adherencebetween the photoelectrode and the ITO-PEN substrate and the connectionbetween the titania beads of the present invention. At last, aphotoelectrode (anode) comprising a titania bead layer was obtained.

Preparation of Dye-Sensitized Solar Cell

Dye-sensitized solar cell was practiced as the embodiment of the presentinvention, in which N719 (Solaronix) was used as the dye comprised inthe cell. 0.05 g of solid N719 was added into 100 mL of ethanol, andstirred and sonicated to obtain a N719 solution having a concentrationof 5×10⁻⁴ M, then the solution was aliquoted and stored in the dark.

The obtained photoelectrode was soaked into the N719 solution for aboutone day, so the time was sufficient for dye to be loaded on the surfaceof the titania product of the present invention. After soaking, thephotoelectrode was removed and soaked into ethanol for about 10 minutesin order to remove the extra dye aggregates. After that, thephotoelectrode was removed and dried, and ready for cell assembly.

A counter electrode (cathode) was prepared separately. A vacuum platinumcoater (JEOL 1600) was used to coat Pt on an ITO-PEN substrate with acurrent of 20 mA for 200 seconds. And, an electrolyte was prepared byMPN (Alfa Aesar, 99%) as a solvent, and 0.1M LiI (Aldrich, 99.99%),0.05M I₂ (Aldrich, 99.999%), 0.5M TBP (Aldrich, 99%) and 0.6M DMPII(Solaronix).

At last, the dye-sensitized solar cell was assembled. A spacer withpores (Surlyn) and having a thickness of 60 μm and a width of 0.6 cm wasplaced on the substrate of the photoelectrode, and then covered by thecounter electrode, so that the two pores on the spacer were located onthe diagonal line of the photoelectrode for injecting electrolytetherein. When all elements were set at the correct positions, thephotoelectrode, spacer and counter electrode were fixed by clamps andheated to melt the spacer and adhere the upper and lower electrodes. Theassembly was then cooled naturally and then the electrolyte wasinjected. After electrolyte injection, the pores of the spacer weresealed to avoid the evaporation of electrolyte, which may causedegeneration of the cell. When the cell assembly was completed, the cellwas objected to the determination of cell efficiency.

The following examples are provided to elucidate the present invention,not to limit the scope of the present invention. Those skilled in theart will recognize and understand them without further explanation. Allthe references are hereby incorporated by reference in its entiretyherein.

EXAMPLES Example 1 Analysis of the Titania Products of the PresentInvention

A series of titania products were prepared by using different amount ofsteric agent (0.25 g, 0.50 g or 0.75 g) and heating at differenttemperature (120° C., 160° C. or 200° C.) in water-heating treatment.These titania products were labeled with the letter “H” to show thatthere were obtained after water-heating treatment. For example, “H 0.25120” represents the titania product prepared by using 0.25 g of stericagent (hexamine) and heating at 120° C. in water-heating treatment bythe preparation method of the present invention.

I. Crystal Structure Analysis of the Titania Product of the PresentInvention

The titania products of the present invention were objected to XRD phaseidentification and electron microscope analysis to identify if theseproducts had a long-range order crystal structure, namely, the structureof anatase titania.

First, the titania products of the present invention were separatelydried at 60° C. for one day to remove water and volatile organiccompounds, thereby reducing the noise of data. Then the dried titaniaproducts prepared under a variety of process parameters were separatelydetected by X-ray diffraction (XRD) in Rigaku D-max XRD with Cu-K_(a)radiation having a wavelength of 0.154 nm as the incident light, a scanrange (two theta) of 20° to 80°, and the scanning rate of 3° per minute.

FIG. 1(A) shows the XRD diffraction diagrams of the sol-gel productsobtained by using different amount of steric agent (withoutwater-heating treatment, labeled with the letter “S”). Regardless of theamount of steric agent, all diffraction diagrams have no diffractionpeak, and this shows that all sol-gel products have an amorphousstructure, not a long-range order structure.

In FIGS. 1(B)-1(D), the XRD diagrams show that the crystal structures ofall titania products of the present invention are the same regardless ofthe amount of steric agent and the temperature of water-heatingtreatment. After comparison with JCPDS 11-1272, the peak of these XRDdiagrams was identified as the diffraction peak of anatase titania, inwhich the highest main peak was the (101) face of anatase, and the twotheta was located at 25.3°. This result completely matches the JCPDSstandard, which shows that the titania product of the present inventionis anatase titania with a long-range order structure not stretched orpressed by additional stress. In this study, the amount of steric agentdoes not affect the crystal structure of the titania products of thepresent invention because the diffraction peak strength, the full widthat half maximum (FWHM) and the diffraction angle of these products arealmost the same, and it also proves that hexamine does not embed intothe structure of TiO₂ (O—Ti—O). That is to say, hexamine is not involvedin the chemical reaction, and it is a true steric agent.

However, both the diffraction peak strength and FWHM are differentbetween the titania products obtained by heating different temperaturesin water-heating treatment. In FIG. 3(A), for example, the diffractiondiagrams of the titania products obtained by using 0.75 g of stericagent and heating at different temperatures in water-heating treatmentare compared, and it is found that when the temperature of water-heatingtreatment increases, the strength of the (101) peak and other peaksincreases, and the FWHM narrows. In other words, the crystallinity ofthe anatase titania powder increases when the temperature increases. Inaddition, Debye-Scherrer equation is used to evaluate the grain size ofthe titania products obtained under a variety of process parameters, andit is found that when the temperature of water-heating treatmentincreases, the grain size also increases (14 nm, 18 nm, 20 nm)—these aresize of monocrystalline nanoparticles suitable for manufacturingphotoelectrode of cells. XRD values and grain sizes are shown in Table1.

TABLE 1 XRD value and grain size of titania products obtained under avariety of process parameters Grain size of Diffraction angle two FWHMof (101) peak Sample theta of (101) peak (°) (101) peak (nm) H 0.25 12025.30 0.572 14.2 H 0.25 160 25.28 0.464 17.5 H 0.25 200 25.30 0.407 20.0H 0.50 120 25.32 0.581 14.0 H 0.50 160 25.31 0.462 17.6 H 0.50 200 25.300.404 20 H 0.75 120 25.29 0.576 14 H 0.75 160 25.32 0.455 18 H 0.75 20025.30 0.411 20

The inventors observed the diffraction diagrams of these productsobtained after water-heating treatment, and found that there wereslightly rises and falls around 31°. After comparison with JCPDS29-1360, it was identified as (121) face of brookite, located at 30.8°(data not shown). After integration calculation, it was found thecontent of brookite in all products was less than 1%, which did notshift the diffraction peak of anatase, and so it could be recognized asa noise. In other words, the powder obtained in this study can berecognized as pure anatase, and this crystal structure is suitable formanufacturing a photoelectrode of cells.

Moreover, JEOL JEM 2100F high-resolution transmission electronmicroscope (HRTEM) was used to identify the crystal structure of thesepowders. The HRTEM image of sample “H 0.75 200” is shown in FIG. 2, inwhich the parallel black lines represent the location of crystal faces.After magnification measurement, it is found the distance between thesefaces (d) is 0.35 nm, the same as that of the (101) face of anatase. Thesquare represents the connection of two grains, and it shows that the(101) faces of two grains attach in the same direction, which means anoriented attachment is formed. When the temperature of water-heatingtreatment is 160° C., an excellent oriented attachment is obtained; andwhen the temperature of water-heating treatment is low (120° C.), thecrystallinity of the product is low and amorphous structure is formed(data not shown). The above HRTEM data shows that the proportion ofamorphous structure reduces when the temperature of water-heatingtreatment increases, and this result is fully supported by XRD results.

II. Crystal Structure Analysis of the Titania Layer of the PresentInvention

The titania products of the present invention and/or a commercialtitania powder (P25 or ST41) were used to prepare the titania layers ofphotoelectrodes as foresaid, and Rigaku D-max2500 XRD was used toanalyze their crystal structures. Rigaku D-max2500 XRD is similar toRigaku D-max XRD, but it is equipped with wide-angle function, andcapable for glancing incident angle diffraction, so the extra signalsfrom the substrate can be eliminated. Therefore, it is suitable foranalyzing thin-film samples, especially the thin-film samples having athickness of 2 μm or less.

The mesoporous titania beads prepared by using 0.75 g of steric agentand heating at different temperature at the water-heating treatment andthe commercial titania powders ST41 and P25 were independently used toprepare a layer made of TiO₂ of photoelectrode, and then objected to XRDanalysis. The results are shown in FIGS. 3A and 3B.

Similar with the foresaid crystal structure analysis, when thetemperature of water-heating treatment increases, the crystallinity ofthe obtained mesoporous titania beads of the present invention alsoincreases. After comparison with JCPDS 21-1272, it was found that themesoporous titania beads of the present invention still had an anatasestructure, and their diagrams were same as the commercial anatasetitania powder ST41. ST41 had an obviously better crystallinity than themesoporous titania beads of the present invention, but it was asubmicron scale powder, and not suitable for manufacturing thephotoelectrode of cells. In addition, after comparison with JCPDS21-1276, it was also found that the commercial titania powder P25 has aproportion of rutile structure with the main diffraction peak of (110)face at 27.4°, as described in the instruction sheet of manufacturer(data not shown). So the P25 powder was also not suitable formanufacturing the photoelectrode of cells. The XRD data and grain sizeof these layers made of the titania products of the present inventionare listed in Table 2. From these data, it is clear that the tendency ofincreased temperature in water-heating treatment results in increasedgrain size is the same. Meanwhile, it also proves that the crystalstructure of the titania product of the present invention does notchange even after the titania product is manufactured as a thin-film ofphotoelectrode.

TABLE 2 XRD value and grain size of the layers prepared by the titaniaproducts of the present invention Grain size of Diffraction angle twoFWHM of (101) peak Sample theta of (101) peak (°) (101) peak (nm) H 0.25120 25.30 0.572 14.2 H 0.25 160 25.28 0.464 17.5 H 0.25 200 25.30 0.40720.0 H 0.50 120 25.32 0.581 14.0 H 0.50 160 25.31 0.462 17.6 H 0.50 20025.30 0.404 20 H 0.75 120 25.29 0.576 14 H 0.75 160 25.32 0.455 18 H0.75 200 25.30 0.411 20

The oxygen vacancy concentration can be calculated through detecting thecontent of Ti³⁺ in the titania products of the present invention (datanot shown), thereby evaluating the proportion of defects caused byoxygen vacancy concentration. Relatively, surface oxygen vacancy carriespositive charges, and results in trap states to stop electronimmigration. The inventors have found that the beads prepared at ahigher temperature in water-heating treatment not only have an increasedcrystallinity of anatase, but also have a reduced oxygen vacancyconcentration, which are advantageous for the following manufacture ofphotoelectrode and cells.

III. Morphology Analysis of the Titania Product of the Present Invention

JEOL 6701F scanning electron microscope (SEM) was used to identify theshape and size of the titania products of the present invention.

FIG. 4 shows the SEM images of the titania products of the presentinvention prepared by using different amount of steric agent and heatingat 200° C. in water-heating treatment, in which (A) H 0.25 200 has anirregular shape; and (B) H 0.50 200 and (C) H 0.75 200 have formedanalogous spheres, also named as “bead” herein. In addition, when theamount of steric agent increases, the surface roughness of the beadsreduces, which means the steric agent helps the formation of spherestructure. The shape of H 0.75 200 is more closed to a sphere than H0.50 200, and the distance between the analogous spheres of H 0.75 200is obviously increased. This is also supported by the other titaniaproducts of the present invention obtained under other processparameters. Comparing with the amorphous sol-gel products (S) preparedby using different amount of steric agent (data not shown), the titaniaproducts of the present invention generally maintain the morphology ofsol-gel products (irregular or analogous sphere), but they are allcrystallized to be anatase titania, their atomic arrangement is changedfrom disorder structure into long-range order structure, and a newsurface is formed. The temperature of water-heating treatment affectsthe bead size, as shown in Table 3.

TABLE 3 Bead diameter of the titania products of the present inventionSize of sol-gel Size of beads Sample products (nm) (nm) H 0.75 120 375375 H 0.50 160 250 250 H 0.75 160 375 750 H 0.50 200 250 250 H 0.75 200375 500 *The sizes of the mesoporous titania beads of the presentinvention are diversely distributed, and the data in Table 3 are averagevalues. The real size range is about ±50-±100 nm.

The above results show that even the steric agent does not affect thecrystal structure, but its molecular structure provides an effectivespace between the analogous sphere beads. Comparing with the mostwell-known steric agent used in the art is hexadecylamine (HAD), thesteric agent used in the present invention, hexamine, is a tertiaryamine in which the nitrogen atoms are shielded by carbon atoms, and notreact with the structure of titania (O—Ti—O), thereby avoiding extradoping and disadvantageous influences to the crystal structure of theproduct given after water heating treatment. Therefore, hexamine shouldbe a better steric agent. Furthermore, the amount of steric agentaffects the shape, size and surface structure of the titania particles.If the amount of steric agent is not enough, irregular nanoparticleswill be formed as the final product, and the beads will not be formed.

IV. BET Analysis of the Titania Product of the Present Invention

Micromeritics ASAP2010 physisorption analyzer was used to proceedBrunauer-Emmett-Teller analysis (BET analysis) to the titania productsof the present invention, in which the absorption and desorption ofnitrogen were detected under a vacuum degree of 10⁻³ ton or less and atemperature of 77K (liquid nitrogen) to analyze the specific surfacearea, pore radius, pore volume, porosity and the like of the samples.The data are shown in the following Tables 4 and 5.

TABLE 4 BET analysis result of the titania products of the presentinvention obtained by heating at different temperatures in water-heatingtreatment Specific surface Pore radius Pore volume Porosity Sample area(m²/g) (nm) (cm³/g) (%) S 0.75 180 2.5 0.11 30 H 0.75 120 95 11.6 0.2751 H 0.75 160 69 16.0 0.27 51 H 0.75 200 62 16.1 0.25 49 P25 55 9.7 0.1334

TABLE 5 BET analysis result of the titania products of the presentinvention obtained by using different amount of steric agent Specificsurface Pore radius Pore volume Porosity Sample area (m²/g) (nm) (cm³/g)(%) S 0.25 182 2.4 0.10 28 S 0.50 180 2.5 0.11 30 S 0.75 180 2.5 0.11 30H 0.25 200 63 16.5 0.26 50 H 0.50 200 62 17.7 0.27 51 H 0.75 200 62 16.10.25 49

Specific surface area affects two factors important to cell efficiency,that is, the dye loading and light harvesting of dye-sensitized solarcells. Generally speaking, nanoparticles have greater specific surfacearea and can be applied to more applications. From the above Tables 4and 5, however, it is found that the sol-gel products have a highspecific surface area, but they are amorphous and not suitable for cellapplications. Usually, pore radius has a negative correlation withspecific surface area, and blocks the mass transfer of dye andelectrolyte. But the pores (mesopore in the present invention) of thetitania beads have greater pore radius and volume than P25. For example,H 0.75 200 of the present invention has a specific surface area similarwith P25, but its pore size and volume are almost twice than those ofP25. This is resulted from the difference in their structure. Inaddition, the mesoporous titania bead of the present invention has aporosity of about 50%, which is suitable for manufacturingphotoelectrodes.

From the data shown in Table 5, it is found that the amount of stericagent does not obviously affect the specific surface area and poreradius of the titania products of the present invention, which means, itdoes not affect the morphology of the beads. Additionally, themicroscopic observation has proved that although H 0.25 200 is ananoparticle, but it has a pore volume similar with that of beads. Thatis to say, although H 0.25 200 has an irregular structure, it hasmesopores.

Example 2 Preparation of Dye-Sensitized Solar Cells with an ElectrodeManufactured by Using the Titania Product of the Present Invention andP25 Powder and Efficiency Analysis thereof

The dye-sensitized solar cells comprising a photoelectrode shown inTable 6 were manufactured as foresaid. The structure of thesephotoelectrodes is shown in FIG. 5(A), which is a well-known structureof dye-sensitized solar cells, comprising two layers made of titania,wherein the first one is scattering layer (bead layer) and the secondone is a titania nanoparticle layer (P25 layer). In Table 6,photoelectrode A merely comprised a titania nanoparticle layer composedof pure P25, no scattering layer was comprised. Photoelectrode Bcomprised a titania nanoparticle layer composed of pure P25 and ascattering layer composed by pure P25, so it was substantively equal toa pure P25 nanoparticle layer of 8 μm. In photoelectrode C-G, the secondlayer was composed of the titania products of the present invention, inwhich the second layer of photoelectrodes C-F was prepared by coatingthe titania bead of the present invention on photoelectrode A, and thesecond layer of photoelectrode G was prepared by H 0.25 200 which wasnot in form of bead, but in form of nanoparticle (irregular shape underSEM observation). The labels of the titania products of the presentinvention are as foresaid described.

The cell efficiency (η) of the above-mentioned dye-sensitized solarcells was measured by the standard method for measuring dye-sensitizedsolar cell efficiency, in which solar simulator was used with parameterset at AM 1.5 G to mimic the cell expression under true sun light. Inaddition, a power supply was used to provide an applied voltage to thedye-sensitized solar cell of the present invention in order to detectthe resulted photocurrent. The applied voltage was changed to mimic theexpression of cell under load, thereby calculating the cell efficiency(η), as shown in Table 6.

Furthermore, the dye-loaded photoelectrodes were soaked in an alkalisolution (such like 0.1M NaOH in ethanol) for about 1 hour to deabsorbthe dye, and the resulted solution was objected to analysis by UV-visspectrometer for calculating the dye loading. The results are shown inTable 6.

TABLE 6 Result of titania layers of photoelectrode prepared by using P25powder alone or using the titania product of the present invention andP25 powder 1^(st) 2^(nd) Bead Cell layer layer size Dye loadingefficiency η Sample (3 μm) (5 μm) (nm) (×10⁻⁷ mol/cm²⁾ (%) A P25 — —0.87 3.21 B P25 P25 — 2.37 4.29 C P25 H 0.75 120 375 4.85 4.57 D P25 H0.75 160 750 4.64 5.01 E P25 H 0.75 200 500 4.52 5.48 F P25 H 0.50 200250 4.48 4.84 G P25 H 0.25 200 NPs 4.32 4.55 NPs: nanoparticles (notbeads)

In Cells A-G, as shown in Table 6, it is found that Cell A has thelowest efficiency (3.21%), and Cell E has the highest efficiency (5.5%).The main difference between Cells A and B is the thickness ofphotoelectrode, so the dye loading is obviously different—Cell B has agreater dye loading, which is able to produce more electrons and resultsin a better efficiency (4.29%). The two-layer structures of Cells B-Ghave the same thickness of photoelectrode, but Cells C-G with a secondlayer made by the titania product of the present invention have a higherefficiency than Cell B with a second layer made by P25 only.Particularly, the cell efficiency of Cell E is higher than higher thanCell B by nearly 30%, and it is 1.7 times of Cell A. These data showthat the scattering layer of photoelectrode prepared by the mesoporoustitania beads of the present invention dramatically increases the cellefficiency.

Furthermore, the dye-loading of Cells C-G is about twice of Cell B (datanot shown), and this is related to the higher specific surface area andpore volume of the titania products of the present invention. Greaterdye-loading means the cell is capable of absorbing more light to producemore electrons. FIG. 5(C) is the amplified schematic illustration of theP25 layer and the titania layer of the present invention in Cells C-G.When the particles/beads are normally piled up, the space between thetitania beads of the present invention is greater, which is easy toaccommodate dye or electrolyte, but the titania nanoparticles comprisedin the beads are contact and orientedly attached. The photoelectrodeusing the mesoporous titania bead of the present invention has abouttwice dye loading than that made of ST 41 that is generally used for thescattering layer of photoelectrode (data not shown).

Cells C-G using the titania beads of the present invention does not havean apparent difference in dye loading, but they do have an obviousdifference in cell efficiency: the lowest is Cell G (4.55%), and thehighest is Cell E (5.48%). It shows that different amount of stericagent and different temperature of water-heating treatment give thetitania products different crystallinity, bead size and surface oxygenvacancy concentration in the present invention, and all thesecharacteristics affect cell efficiency.

This example provides a two-layer titania structure prepared by themesoporous titania beads of the present invention and commercial titaniananopowder P25 (i.e., bead layer and nanoparticle layer), and thetitania nanoparticle layer can be prepared by any nano-scale titaniapowder.

Example 3 Preparation of Dye-Sensitized Solar Cells with an ElectrodeManufactured by Using the Titania Product of the Present Invention Aloneand Efficiency Analysis thereof

The dye-sensitized solar cells comprising a photoelectrode shown inTable 7 were manufactured as foresaid, wherein the structure of thesephotoelectrodes is shown in FIG. 5(B). Photoelectrode O was composed ofthe nanoparticle H 0.25 200, which was not in form of bead.Photoelectrodes H-N were prepared by using the mesoporous titania beadof the present invention alone. Sample B was the control. The labels ofthe titania products of the present invention are as foresaid described.

TABLE 7 Result of titania layers of photoelectrode prepared by using thetitania product of the present invention alone thick- Bead Cell Photo-ness size Dye loading efficiency η Sample electrode (μm) (nm) (×10⁻⁷mol/cm²⁾ (%) B P25 8 — 2.37 4.29 H H 0.75 120 7.5 375 5.60 3.16 I H 0.75160 2.7 750 1.90 2.63 J H 0.75 160 5.2 750 3.64 3.69 K H 0.75 160 7.8750 5.48 4.03 L H 0.75 160 10.0 750 6.84 3.53 M H 0.75 200 7.6 500 5.284.92 N H 0.50 200 7.8 250 5.12 4.74 O H 0.25 200 7.8 NPs 4.96 4.56 NPs:nanoparticles (not beads)

In Cells I, J, K and L, which uses the same bead (H 0.75 160 with beadsize of 750 nm) with different thickness of titania layer, the best cellefficiency does not go to Cell L having the thickest titania layer, butto Cell K having a thickness of 7.8 μm; and the cell efficiency of CellK is close to Cell B having a photoelectrode prepared by pure P25 withan equal thickness (8 μm). Regarding with Cells H-O prepared by thetitania product of the present invention alone, the lowest cellefficiency goes to Cell H (3.16%), and the highest goes to Cell M(4.92%); and the cell efficiency of Cell M is higher than Cell B of pureP25 by nearly 15%. In addition, the dye loading of the mesoporoustitania beads of the present invention can be 2-3 times of P25 (Cell B).

In the flexible cell applications, the best thickness of titania layeris generally not over 10 μm. Thus, it is obvious that the mesoporoustitania beads of the present invention can be applied to the flexiblecells, especially to dye-sensitized solar cells.

Example 4 Preparation of Dye-Sensitized Solar Cells with an ElectrodeManufactured by Using the Mixture of the Titania Product of the PresentInvention and P25 Powder and Efficiency Analysis thereof

The dye-sensitized solar cells comprising a photoelectrode shown inTable 8 were manufactured as foresaid, wherein the structure of thesephotoelectrodes is shown in FIG. 5(B). Photoelectrodes Q-S were preparedby the mixture of H 0.75 160 and P25 at a specific ratio into a layerwith a specific thickness. Photoelectrodes T-V were prepared by themixture of one of the H 200 series and P25 at a specific ratio into alayer with a specific thickness. Samples B and K were controls. Thelabels of the titania products of the present invention are as foresaiddescribed.

TABLE 8 Result of titania layers of photoelectrode prepared by using themixture of titania product of the present invention and P25 TiO₂ bead ofFinal Dye Cell the present bead loading efficiency Sam- P25 inventionthickness size (×10⁻⁷ η ple (wt %) (wt %) (μm) (nm) mol/cm²⁾ (%) B 100 — 8.0 — 2.37 4.29 K — 100  7.8 750 5.48 4.03 (H 0.75 160) P 75 25 7.5375 3.08 2.97 (H 0.75 120) Q 25 75 7.0 750 4.50 1.88 (H 0.75 160) R 5050 7.4 750 3.73 2.62 (H 0.75 160) S 75 25 7.7 750 2.95 3.01 (H 0.75 160)T 75 25 7.6 500 2.84 3.21 (H 0.75 200) U 75 25 7.5 250 2.72 3.00 (H 0.50200) V 75 25 7.5 NPs 2.63 3.25 (H 0.25 200) NPs: nanoparticles (notbeads)

In the preparation of Cells Q-S, the beads of H 0.75 160 (with bead sizeof 750 nm) were mixed with P25 with a specific proportion of 75%, 50%and 25%, respectively. Comparing with Cell K using pure H 0.75 160 asthe photoelectrode, Cells Q-S have a dramatically reduced cellefficiency. This shows that the mixtures of the mesoporous titania beadof the present invention and P25 gave a cell efficiency lower than purebead, and Cell S having a lower bead content (25%) provides a relativelyhigh cell efficiency (3.01%). The dye loading increases when the beadcontent increases (data not shown), which demonstrates that P25 does notfill in the space between beads. However, the other mixture of a varietyof titania products of the present invention and P25 have similar cellefficiency according to data shown in Table 8, which means the interfacebetween P25 and the titania products of the present invention consumeselectrons, and eliminates the difference between these materials.

In summary, these examples clearly elucidate that the present inventionprovides a two-step method for preparing a mesoporous titania bead, andthe mesoporous titania bead prepared by the method. Said mesoporoustitania bead increases cell efficiency. When the thickness of thephotoelectrode is 8 μm, the titania nanoparticle layer made by pure P25increases cell efficiency by 4.3%; the combination with a mesoporoustitania bead layer of the present invention increases cell efficiency by5.5%, which is about 30% higher; and the titania layer made by themesoporous titania bead of the present invention alone increases cellefficiency by 5%, which is about 20% higher. From above, it should beclear that a photoelectrode with higher crystallinity and lower surfaceoxygen vacancy concentration helps electron diffusion and reduces therecombination, thereby increasing electron collection efficiencydramatically. In addition, although larger bead provides higher lightharvesting efficiency, but it also causes more back-scattering, and theelectron injection efficiency reduces because the extra dye stays in thespace between beads; however, the increase of light harvesting isgreater than the reduce of electron injection efficiency, as well as thefast electron diffusion resulted from anatase titania and the orientedattachment, the cell efficiency is still higher than the traditionaltechnology. From the data of the present invention, the best titaniabead for photoelectrode has a bead size of 500 nm with highcrystallinity and low surface oxygen vacancy concentration because itresults in more back-scattering and good dye-loading.

We claim:
 1. A photoelectrode, comprising: (1) a substrate; and (2) atitania layer composed of a mesoporous titania bead having a diameter of200-1000 nm, specific surface area of 50-100 m²/g, porosity of 40-60%,pore radius of 5-20 nm, pore volume of 0.20-0.30 cm³/g, and the titaniacomprised in the bead is anatase titania.
 2. The photoelectrodeaccording to claim 1, wherein said substrate is a metal substrate, or atransparent non-conductive substrate covered by a transparent conductivefilm.
 3. The photoelectrode according to claim 1, wherein said titanialayer has a thickness of 5-10 μm.
 4. The photoelectrode according toclaim 1, wherein said mesoporous titania bead is prepared by thefollowing steps: (1) adding a steric agent and a titanium-containingprecursor into ethanol to proceed sol-gel reaction and give a sol-gelproduct, wherein the molar ratio of said steric agent:saidtitanium-containing precursor:ethanol is 0.1-1:1:200-300; and (2)heating said sol-gel product in water at 120-200° C. for 1-24 hours toobtain the mesoporous titania bead.
 5. The photoelectrode according toclaim 4, wherein said steric agent is a tertiary amine.
 6. Thephotoelectrode according to claim 5, wherein said tertiary amine isselected from hexamine, trimethylamine, quinoline, isoquinoline ormethyldiethylamine (CH₃N(CH₂CH₃)).
 7. The photoelectrode according toclaim 4, wherein said titanium-containing precursor is selected fromtitanium tetraisopropoxide, titanium tetrachloride, titaniumtrichloride, ethyl orthotitanate or Ti(OC₄H₈)₄.
 8. The photoelectrodeaccording to claim 4, further comprising adding a salt into said ethanolin step (1) to adjust ionic strength to 1×10³¹ ⁴-32×10⁻⁴.
 9. Thephotoelectrode according to claim 8, wherein said salt is selected fromKCl, LiCl, NaCl, KCl, LiF, NaF, KF, LiBr, NaBr, KBr, LiI, NaI, KI, CsCl,CsI, CsBr, KNO₃.
 10. The photoelectrode according to claim 1, whereinsaid titania layer increases scattering efficiency and used as ascattering layer.
 11. The photoelectrode according to claim 1, furthercomprising a titania nanoparticle layer between said substrate and saidtitania layer.
 12. The photoelectrode according to claim 11, whereinsaid titania nanoparticle layer is composed of a titania nanoparticle,not composed of said mesoporous titania bead.
 13. The photoelectrodeaccording to claim 12, wherein said titania nanoparticle of the titaniananoparticle layer is P25, ST-01, ST-21, ST-31, TTO-55S or ST-30L. 14.The photoelectrode according to claim 1, which is used for manufacturinga cell.
 15. A method for preparing the photoelectrode according to claim1, comprising: (4) providing a substrate; (5) coating a mesoporoustitania bead on said substrate to obtain a coated layer, in which saidbead has a diameter of 200-1000 nm, specific surface area of 50-100m²/g, porosity of 40-60%, pore radius of 5-20 nm, pore volume of0.20-0.30 cm³/g, and the titania comprised in the bead is anatasetitania; and (6) pressing the coated layer from step (2) under roomtemperature to obtain said titania layer.
 16. The method according toclaim 15, wherein said substrate is a metal substrate, or a transparentnon-conductive substrate covered by a transparent conductive film. 17.The method according to claim 15, further comprising the following stepbetween step (1) and step (2): coating a titania nanoparticle on saidsubstrate to obtain a titania nanoparticle layer, and said titaniananoparticle is not said mesoporous titania bead.
 18. The methodaccording to claim 15, which is applied to cell manufacture.